Process for breaking petroleum emulsions



l 'atented Feb. 20, 1951 UNITED STATES PATENT OFFICE PROCESSES FOR BREAKING PETROLEUM EMULSIONS Melvin DeiGroote, University City, andBernhard Keiser, Webster Groves, Mm, assignors to'P'etro lite=Corporation, Ltd Wilmington, DeL, a cor pox-ation of Delaware NoDrawing. Application December 13', 1948,

Serial No. 65,090

11 Claims. (Cl. 252-341) ruary 16, 1-948 mow abandonedi, and also serialNo; 82,704; filed *Ma'r'chZl, 1949, nowissued as Patent No; 2,499,370;dated March 7, 1950. Attention is also directed to our co-pending'application Serial- No'. 65,688, filed December 13, 19481 Complementaryto the above aspect of the incvention', is our companion inventionconcerned with the new chemical roducts or compounds used as thedemulsifying agents in said aforementioned processes or" procedures, aswell as the application of such chemicai compounds; products, and thelike, in various other" arts and industrie's, alongwith the methods formanufacturing' said n'ew'ch'emical products or compounds 1 which are ofoutstanding value in demulsification. See our co-p'endi'ng applicationSerial No. 65,09l-, filed December 13, 1948.

Our invention provides an economical and rapid process for resolvingpetroleum emulsions of the water in-oiLtype, that are commonly referredto as cut oil, roily oil, emulsified oil, etc, and which comprises finedroplets of naturally-occurring waters-or brines dispersedin a more orless permanent state throughout theoil which constitutes the continuousphase of the emulsion.

"It also provides an economical and rapid 'process for separatingemulsions which have been prepared under controlled conditions from min-I eral oil, such as crude oil and relatively soft waters or weak brines.Controlled emulsification and subsequent demulsification, under theconditions. just mentioned, are of significant value in removingimpurities, particularly inorganic salts, from pipeline oil. v I

Demulsification as contemplated: in the present application, includesthe preventive step of commingling the demulsifler with the aqueouscomponent which would or might subsequently become either phase of theemulsion, in'theabsence of such precautionary measure. Simi1arly,

I ated' derivatives of certain resins hereinafter specified.

Thus, the present process is concernedwith breaking: petroleum emulsionsof the water-inoil type, characterized by subjecting the emulsion to thehydrophile quaternary ammonium compounds hereinafter described. Saidhydro-' phile quaternary ammonium compounds are obtained by reactionbetween a dimethylated higher aliphatic amine, in which the aliphaticradical has at least 10 and not more than 22 carbon atoms, and the esterof an alpha-halogen monocarboxylic acid having not over 6 carbon atomsand hydrophile hyd'roxylated synthetic products; said hydrophilesynthetic products being oxyalkylationproducts oi (A) an alpha-betaalkylene oxide having not more than 4 carbon atoms and selected: fromthe class consisting of ethylene oxide, propylene oxide, butylene oxide,glycide, and m'ethylglycide; and (B) an oxyalkylationsusceptible,fusible, organic solvent-soluble, water-insoluble, phenol-aldehyderesin; said resin being derived by reaction between a difunctional'monohydric phenol and an aldehyde having not over 8- carbon atoms andreactive towards said phenol; said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula:

in which R is ahydrocarbonradical having at divalent-radicals having theformula (R-iOh in a which R1 is a member selected from the classconsisting of ethylene radicals, propylene radicals, butylene radicals,hydroxypropylene radicals, and hydroxybutylene radicals, and n is anumeral varying from 1 to 20; with the proviso that at least 2 moles ofalkylene oxide be introduced for each phenolic nucleus; and with thefinal proviso that the hydrophile properties of the ultimate quaternaryammonium compound as well as the oxyalkylated resin in an equal weightof xylene are sufficient to produce an emulsion when said xylenesolution is shaken vigorously with one to three volumes of water.

For convenience, what is said hereinafter may be divided into fiveparts. Part 1 will be concerned with the production of the resin from adifunctional phenol and an aldehyde; Part 2 will be concerned with theoxyalkylation of the resin so as to convert it into a hydrophilehydroxylated derivative; Part 3 will be concerned with the conversion ofthe immediately aforementioned derivative into a total or partial esterby reaction with chloroacetic acid, or the like; Part 4 will beconcerned with a reaction between such esters containing a labilehalogen and the dimethylated higher aliphatic amines of the kindpreviously described; and Part 5 will be concerned with the use of suchquaternary ammonium compounds, as hereinafter described.

PART 1 .As to the preparation of the phenol-aldehyde resins reference ismade to our co-pendingapplications, Serial Nos. 8,730 and 8,731, bothfiled February 16, 1948, both now abandoned. In such co-pendingapplications we described a fusible, organic solvent-soluble,water-insoluble resin polymerof the formula the'resin is fusible andorganic solvent-soluble.

R is a hydrocarbon radical having at least 4 and 4 expensive and higheraldehydes are both less reactive, and are more expensive. Furthermore,the higher aldehydes may undergo other reactions which are notdesirable, thus introducing difficulties into the resinification step.Thus acetaldehyde, for example, may undergo an aldol condensation, andit and most of the higher aldehydes enter into self-resinification whentreated with strong acids or alkalies. On the other hand,higheraldehydes frequently beneficially affect the solubility andfusibility of a resin. This is illustrated, for example, by thedifferent characteristics of the resin prepared from para-tertiaryamylphenol and formaldehyde on one hand, and a comparable productprepared from the same phen'olic reactant and heptaldehyde on the otherhand. The former, as shown in certain subsequent examples, is a hard,brittle, solid, whereas the latter is soft and, tacky, and obviouslyeasier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. Theemployment of furfural requires careful control for the reason that inaddition to its aldehydic function, furfural can form vinylcondensations by virtue of its unsaturated structure. The production ofresins from furfural .for use in preparing reactants for the presentprocess is most conveniently conducted with weak alkaline catalysts andoften with alkali metal carbonates. Useful aldehydes, in addition toformaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde,2-ethylhexana1, ethylbutyraldehyde, heptaldehyde, and benzaldehyde,furfural and glyoxal.

is tetrafunctional. been that, in resin manufacture and particularly asdescribed herein, apparently only one of the aldehydic functions entersinto the resinification reaction; The inability of the other aldehydicout theuseof any catalyst at all. Among theuse ful alkaline catalystsareammonia, amines, and

quaternary ammonium bases. It is generally accepted that when ammoniaand amines are emnot over 8 carbon atoms. In the instant application Rmay have as many as 12 carbon atoms, as in the case ofa resin obtainedfrom a dodecylphenol. In the instant invention it may be first suitableto describe the alkylene oxides employed as reactants, then thealdehydes, and finally the phenols, for the reason that thelatterrequire a more elaborate description.

The alkylene oxides which may be used are the ployed as catalysts theyenter into the condensation reaction and, in fact, may operate byinitial combination with the aldehydic reactant. Thef compoundhexamethylenetetramine illustrates such a combination. In light of thesevarious reactions it becomes difiicult to present any formula whichwould depict thestructure of the various alpha-beta oxides having notmore than 4 carbon V atoms, to wit, ethylene oxide, alpha-beta propyleneoxide, alpha-beta butylene oxide, glycide, and methylglycide.

Any aldehyde capable offorming a methylol or a substituted methylolgroup and having not more than 8 carbon atoms is satisfactory, so lon asit does not possess some other functional group or structure whichwill-conflict with the resinification reaction or with the subsequentoxyalkylation of the resin, but the use of formaldehyde, in

its cheapest form of an aqueous solution, for the production of theresins is particularly advanta geo'us. Solid polymers offormaldehyde-are more resins prior to oxyalkylation. More will besaidsubsequently as to the difference between the-use of an alkalinecatalyst and anacid catalyst; even in the use of an alkaline catalystthere is considerable evidence to indicate that the products are" notidentical where different basic materials are weak acids such as'sodiumacetate, etc.

Suitable phenolic'reactants include the following: Paratertiarybutylphenol; para-secondarybutylphenol;para-t'ertiary-amylphenol;' parasecondary amylphenol';pa'ra-tertiaryhexylphenol; para -isooctylphenol;

It would appear that the use of j glyoxal should be avoided due'to thefact that it However, our experience has 1 ortho-phenylphenol;

amaoce Mra-phenylphenol; ortho benzylphenol; parabenzylphenol; andpara-cyclohexylphenol, and the. corresponding ortho-para substitutedmeta-- cresols and 3,5-xylenolsi Similarly, one may usepara-roeortho=nonylphenol or amixture, paraor ortho decylphenol' or a mixture;men-thylpheno or para or ortho-dodecylphenol.

For convenience, the! phenol has previously been referred to asmonocyclio in order to (iii-- ferentiate from fused nucleus polycyclicphenols, such. as substituted naphthols; Specifically, iiionocycliclimited to the nucleus in which the hydroxyl radical is attached.Broadly speak ing}, wherea substituent iecyclic', particularly aryl,obviously in the usual sense such phenol is: actually polycyclicalthough the: phenolic by droxyl is not attached to a. fused. polycyclicnucleus; Stated another phenols in which the hydroxyl group is directlyattached to a com denseu o'i' fus'e'd polycyclic structure, areexcluded. This matter, how'ev'er is clarified by the followirigconsideration. The phenols herein contemplated for reaction maybe'indicated by the following formula:

in which R. is selected fromthe class consisting of hydrogen atomsandhydrocarbon radicals having at least 4 carbon atoms and not more than 12carbon atoms, with the proviso that one occurrence of R is thehydrocarbon substituent and the other two occurrences are hydrogenatoms, and with the further provision that one or both of: the 3 and 5positions may be methyl substituted.

The above formula possibly can be restated more conveniently in thefollowing manner, to wit, that the phenol employed is of the followingformula, with the proviso that R is a hydrocarbon substituent located inthe 2,4,6 position, again with the provision as to 3 or 3,5 methylsubstitution. This is conventional nomenclature, numbering the variouspositions in the usual clockwise manner, beginning with the hydroxylposition as one:

The manufacture of thermoplastic phenol-aldehyde resins, particularlyfrom formaldehyde and a difunctional phenol, i. e., a phenol in whichone of the three reactive positions (2,4,6) has been substituted: by ahydrocarbon roup, and particularly by one having at least 4 carbon atomsand not more than 12 carbon atoms, is well known. As has been previouslypointed out, there is no objection to a methyl radical provided it ispresent in the 3 or 5 position.

Thermoplastic or fusible phenol aldehyde resins are usually manufacturedfor the varnish trade and oil solubility is of prime importance. Forthis reason, the common reactants employed are but-ylated henols.amylated phenols, phenylphenols,.etc.- ,The methods employedmanufacturing such resins are similar to: those em ployed in themanufacture of ordinary phenolformaldehyde resins, in that either anacid or alkaline catalyst is usually employed. The procedure usuallydiffers from that employed in the manufacture of ordinaryphenol-aldehyde resins in that phenol, being water-soluble, reactsreadily with an aqueous aldehyde solution without further difii-culty,while when a waterinsoluble phenol is employed some modification isusually adopted to increase the interiacial surface and thus causereaction to take place. A common solvent issometimes employ iil Anotherprocedure employs rather severe agitation to create a large interfacialarea. Once the reaction starts to a moderate degree, it is possible thatboth reactants are somewhat soluble in the partially reacted mass andassist. in hastening the reaction. We" have found it'd'esirable toemploy a small proportion of an or= gahic sulfo-acid as a catalyst,either alone or along with a mineral acid like sulfuric orhydroclilori'c acid. For example, alkylated aromatic sulfo'nic acids areeffectively employed. Since commercial forms of such acids are commonlytheir alkali salts, it is sometimes convenient to use a small quantityof such alkaliv salt plus a small. quantity of strong mineral acid, asshown. in the. examples below. If desired, such organic sulfo-acids maybe prepared in situ. in the phenol employed, by reacting concentratedsulfuric acid with a small proportion of the phenol. In suchcases wherexylene is used as a solvent and concentrated sulfuric acid is employed,some sulfonation of the xylene probably occurs to produce thesulfo-acid. Addition of a solvent. such as xylene is advantageous ashereinafter described in detail. Another variation of procedure is toemploy such organic sulfo-acids, inthe form of their salts, inconnection with an alkali-catalyzed resinification procedure. Detailedexamples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusibletype of resin by the acid catalytic procedure is that, since adifunctional phenol is employed, an excess of an aldehyde, for instanceformaldehyde, may be employed without too. marked a change in conditionsof reaction and ultimate product. There is usually little,- if any;advantage, however, in using an' excess over and above thestoichiometric propor tions for the reason that such excess may be lostand wasted. For all practical purposes the molar ratio of formaldehydeto phenol may be limited to 0.9 to 1. with 1.05 as the preferred ratio,or sufficient, at least theoretically, to con"- vert the remainingreactive hydrogen atom of each terminal phenolic nucleus. Sometimeswhnhigh aldehydes. are used an excess of ald hydic reactant can bedistilled off and thus re: covered from" the reaction mass. This samepro-- cedure: maybe used with formaldehyde and ex": cess reactantrecovered.

When an alkaline catalyst is used the amount of aldehyde, particularlyformaldehyde, may be increased over the simple stoichiomet'ric ratio ofone-to-one or thereabouts. With the use of al k'aline catalyst it hasbeen recognized that considerably increased amounts of formaldehyde may"be used, as much as two moles of formaldehyde, for example, per mole ofphenol, or even more; with the result that only a small part of suchaldehyde remains unco'mbined or is subsequently li-beratedduri-ngresinification. structures Which have been advanced to explain suchincreased use of aldehydes are the following:

OE OH Such structures may lead to the production of cyclic polymersinstead of linear polymers. For this reason, it has been previouslypointed out that, although linear polymers have by far the mostimportant significance, the present invention does not exclude resins ofsuch cyclic structures.

Sometimes conventional resinification procedure is employed using eitheracid or alkaline catalysts to produce low-stage resins. Such resins maybe employed as such, or may be altered or' converted into high-stageresins, or in any event, into resins of higher molecular weight, byheating along with the employment of vacuum so as to split off water orformaldehyde, or both. Generally speaking, temperatures employed,particularly with vacuum, may be in the neighborhood of 175 to 250 C.,or thereabouts.

It may be well to point out, however, that the 7 amount of formaldehydeused may and does usuallyafiect the length of the resin chain.Increasing the amount of the aldehyde, such as formaldehyde, usuallyincreases the size or molecular weight of the polymer.

In the hereto appended claims there is speventional resinificationprocedure will yield products usually having definitely in excess of 8nuclei. In other words, a'resin having an average of 4, or 5 nuclei perunit is apt to be formed as a minimum in resinification, except undercertain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures,substituting cymene, tetralin, etc., or some other suitable solventwhich boils or refluxes at a higher temperature, instead of xylene, insubsequent examples, and if one doubles or triples the amount ofcatalyst, doubles or triples the time of refluxing, uses a marked excessof formaldehyde or other aldehyde, then the average size of the resin isapt to be distinctly over the above values, for example, it may average7 to units. Sometimes the expression low-stage resin or low-stageintermediate is employed to mean a stage having 6 or 7 units or evenless. In the appended claims we have used low-stage to mean 3 to 7 unitsbased on average molecular weight.

- The molecular weight determinations, of course, require that theproduct be completely soluble in the particular solvent selected as,for" instance, benzene. The molecular weight determination of suchsolution may involve either the freezing point as in the cryoscopicmethod, or, less conveniently perhaps, the boiling point in anebullioscopic method. The advantage of the ebullioscopic method is that,in comparison with the cryoscopic method, it is more apt to insurecomplete solubility. One such common method to employ is that of Menziesand Wright (see J. Am. Any suit-' Chem. Soc. 43, 2309 and 2314 (1921)).able method for determining molecular weights will serve, althoughalmost any procedure adopted has inherent limitations. A good method fordetermining the molecular weights of resins, especially solvent-solubleresins, is the cryoscopic procedure of Krumbhaar which employsdiphenyl-; amine as a solvent (see Coating and Ink Resins, page 157,Reinhold Publishing Co. 1947) Subsequent examples will illustrate theuse of an acid catalyst, an alkaline catalyst, and no cata.yst. As faras resin manufacture per se is concerned, We prefer to use an acidcatalyst, and particularly a mixture of an organic sulfo-acid and amineral acid, along with a suitable solvent, such as xylene,ashereinafter illustrated in detail. However, we have obtained productsfrom resins obtained 'by ;use of an alkaline catalyst which were just assatisfactory as those obtained employing acid catalysts. Sometimes acombination of both types of catalysts is used in different stages ofresinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., thosereferred to as high-" stage resins, are conveniently obtained bysubjecting lower molecular Weight resins to vacuum distillation andheating. Although such procedure sometimes removes only a modest amountor even perhaps no low polymer, yet it it a.most certain to producefurther polymerization. For instance, acid catalyzed resins obtained inthe usual manner and having a molecular weight indicating the presenceof approxi mately 4 phenolic units or thereabouts may bei subjected tosuch treatment, with the result that one obtains a resin havingapproximately The usual prodouble this molecular weight. cedure is touse a secondary step, heating the resin in the presence or absence of aninert gas,

limit specified herein, there may be some tend-' ency to dimerization.The usual procedure to obtain a dimer involves an enormously largeexcess of the phenol, for instance, 8 to 10 moles per mole of aldehyde.Substituted dihydroxydiphenylmethanes obtained from phenols are notresins as that term is used herein.

Although any conventional procedure ordinarily employed may be used inthe manufacture of the herein contemplated resins or, for that matter,such resins may be purchased in the open market, we have found itparticularly de-H sirable to use the procedures described else-.

substituted conveniently in the oxyalkylation stage.

where herein, and employing a combination of an organic sulfo-acid and amineral acid as a catalyst, and xylene as a solvent. By way ofillustration, certain subsequent examples are included, but it is to beunderstood the herein described invention is not concerned with theresins per se or with any particular method of manufacture but isconcerned with the use of reactants obtained by the subsequentoxyalkylation thereof. The phenol-aldehyde resins may be prepared in anysuitable manner.

Oxyalkyation, particularly oxyethylation which is the preferredreaction, depends on contact between a non-gaseous phase and a gaseousphase. It can, for example. be carried out by melting the thermoplasticresin and subjecting it to treatmentwith ethylene oxide or the like, orby treating a, suitable solution or suspension. Since the melting pointsof the resins are often higher than desired in the initial stage ofoxyethylation, we have found it advantageous to use a solution or s sensi n of thermonlastic resin in an inert solvent such as ylene. Undersuch circ mstan es the resin obtained in the usual manner is dissolvedby heating in xylene und r a reflux condenser or in any other suitablemanner. Since xylene or an equivalent inert solvent is pre ent or may bepresent during oxyalky -ation, it is obvious there is no obiection tohaving a sol ent present during the resinifyin stage if, in addition tobeing inert towards the resin, it is 'also inert towards the reactantsand also inert towards water. Numerous solvents, particularly ofaromatic or cyclic nature, are suitably adapted for such use. Examplesof such solvents are xylene, cymene, ethyl benzene, propyl benzene,mesitylene, decalin (decahydronaphthalene), tetralin (tetrahydronaphthaene),

ethylene glycol diethylether, diethylene glycol 'ing, and also becausethe solvent can be employed in connection with a reflux condenser and awater trap to assist in the removal of water of reaction and also waterpresent as part of the formaldehyde reactant when an aqueous solution offormaldehyde is used. Such aqueous solution, of

course, with the ordinary product of commerce containing about 37 /275to 40% formaldehyde, is the preferred reactant. When such solvent isused it is advantageously added at the beginning of the resinificationprocedure or before the re action has proceeded very far.

The solvent can be removed afterwards by distillation with or withoutthe use of vacuum, and a Lfinal higher temperature can be employed to.

"complete reaction if desired. In many instances it is most desirable topermit part of the solvent,

particularly when itis inexpensive, e. g., xylene, to remain behind in apredetermined amount so to have a resin which can be handled more If amore expensive solvent, such as decalin, is employed, xylene or otherinexpensive solvent may be added after the removal of decalin, ifdesired.

In preparing resins from difunctional phenols it is common to employreact-ants of technical grade. The substituted phenols hereincontemplated are usually derived from hydroxybenzen'e. As a rule, suchsubstituted phenols are comparatively free from unsubstituted phenol. Wehave generally found that the amountpresent is considerably less than 1%and not infrequently in the neighborhood of 1% of 1%, or even less. Theamount of the usual trifunctional phenol, such as hydroxybenzene ormet-acresol, which can be tolerated is determined by the fact thatactual cross-linking, if it takes place even infrequently, must not besufficient to cause insolubility at the completion of the resinificationstage or the lack of 'hydrophile properties at the completion of theoxyalkylation stage.

The exclusion of such tri'functional phenols as hydroxybenzene ormetacresol i not based on the fact that the mere random or occasionalinclusion of an unsubstituted phenyl nucleus in the resin molecule or inone of several molecules, for example, markedly alters thecharacteristics of the oxyalkylated derivative. The presence of a.phenyl radical having a reactive hydrogen atom available or having ahydroxymethylol or a substituted hydroxymethylol group present is apotential source of cross-linking either during resinification oroxyalkylation. Cross-linking leads either to insoluble resins or tonon-hydrophilic products resulting from the oxyalkylation procedure.With this rationale understood, it is ob vious that trifunctionalphenols are tolerable only in a minor proportion and should not bepresent to the extent that insolubility is pro- .duced in the resins, orthat the product resulting from oxyalkylation is gelatinous, rubbery, orat least not hydrophile. As to the rationale of resinification, noteparticularly what is said hereafter in difierentiating between resoles,Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organicsolvent-soluble resins are usually linear but may be cyclic. Such morecomplicated structure may be formed, particularly 'if a resin preparedin the usual manner is converted into a higher stage resin by heattreatment in vacuum as previously mentioned. This again is a reason foravoiding any opportunity for cross-linking due to the presence of anyapother words, the presence of such reactant may 'cause cross-linkin ina conventional resinification procedure, or in the oxyalkylationprocedure,

or in the heat and vacuum treatment if it is employed as part of resinmanufacture.

Our routine procedure in examining a phenol for suitability forpreparing intermediates to be used in practicing the invention is toprepare a resin employing formaldehyde in excess (1.2

moles of formaldehyde per mole of phenol) and using an acid catalyst inthe manner described in Example 1a of our Patent 2,499,370 granted March'7, 1950. If the resin so obtained is solvent-soluble in any one of thearomatic or other solvents previously referred to, it is then subjectedl65, C. with addition of at least 2 and advanta eously up to 5 moles ofethylene oxide per phenolic hydrox-yl. .tageously conducted so as torequire from a few two or less reactive hydrogen atoms. what appearsinthese most recent and most up-to-date investigation is pertinent tothe pres- The oxyethylation is advanminutes up to to hours. If theproduct so "obtained is solven-soluble and self-dispersin or ;vent maybe removed prior to the dispersibility or emulsifiability test. When aproduct becomes rubbery during oxyalkylation due to the presence ofjasmall amount of trireactive phenol, as previously mentioned, or for someother reason,.it

may become extremely insoluble, and no longer qualifies as beinghydrophile as herein specified. ,Increasing the size of the aldehydicnucleus, .for

instance using heptaldehyde instead of formaldehyde, increasestolerance. for trifunctional phenol.

.The presence of a trifunctional or tetrafunctional phenol (such asresorcinol or bisphenol A) is apt to produce detectable cross-linkingand insolubilization but will not necessarily do so,

especially if the proportion is small. Resinifica- 'tion involvingdifunctional phenols only may also produce insolubilization, althoughthis seems to be an anomaly or a contradiction of What is someiitimessaid in regard to resinification reactions involving difunctionalphenols only. This is presumably due to cross-linking. This appears tobe contradictory to what one might expect in 'light of the theory offunctionality in resinifica- "tion. "stances, or rather under thecircumstances of conventional resin, manufacture, the proceduresemploying difunctional phenols are very apt to, and almost invariablydo, yield solvent-soluble. fusible resins. However, when conventionalprocedures are employed in connection with resins "for varnishmanufacture or the like, there is I involved the matter of color,solubility in oil, etc.

When resins of the same type are manufactured It is true that underordinary circumfor the herein contemplated purpose, i. e., as a.

'raw material to be subjected to oxyalkylation,

such criteria of selection are no longer pertinent.

conditions of resinification than those ordinarily with the minorreact.ons of ordinary resin manufacture which are'of importance in thepresent invention for the freason that they occur under more drasticconditions of resinification which may be employed advantageously attimes, and

they may lead to cross-linking.

In this connection it may be well to point out that part of thesereactions are now understood A or explainable to a greater or lesserdegree in light of a most recent investigation. Reference is made to theresearches of Zlnke and his co-workers, Hultzsch and his associates, andto von Eulen and his co-workers, and others. As to a bibliography ofsuch investigations, see Carswell, Phenoplasts,

' chapter 2. These investigators limited much of their work to reactionsinvolving phenols having Much of oxyalkylation stage. This situation maybe related ent invention insofar that much of it is referring toresinification involving difunctional phenols.

For the moment, it may be simpler to consider a mo-st typical type offusible resin andforget for the time that such resin, at least undercertain circumstances, is susceptible to further complications.Subsequently in the text. it will be pointed out that cross-linking orreaction with excess formaldehyde may take place even with one of suchmost typical type resins. This point is made for the reason thatinsoluble must be avoided in order to obtain the products hereincontemplated for use as reactants.

The typical type of fusible resin obtained .from a para-blocked orortho-blocked phenol is of the difunctional phenol-aldehyde type resin;

but such addition to a Novolak causes cross-linking by virtue of theavailable third functional position.

What has been said immediately preceding is subject to modification inthis respect: It is well known, for example, that difunctional phenols,for instance, paratertiaryamylphenol, and an aldehyde, particularlyformaldehyde, may yield heat-hardenable resins, at least under certainconditions, as for examplethe use of two moles of formaldehyde to one ofphenol, along with an alkaline catalyst. This peculiar hardening orcuring or cross-linking of resins obtained from difunctional phenols hasbeen recognized by various authorities.

The intermediates herein used must be hydrophile or sub-surface-activeor surface-active as hereinafter described, and this precludes theformation of insolubles during resin manufacture or the subsequent stageof resinmanufacture where heat alone, or heat and vacuum, are employed,or in the oxyalkylation procedure. In its simplest presentation therationale of resinification involving formaldehyde, forexample, and adifunc- 'tional phenol would not be expected to form crosslinks.However, cross-linking sometimes occurs and it may reach theobjectionable stage. However, provided that the preparation of resinssimply takes into cognizance the present knowl edge of the subject, andemploying preliminary, exploratory routine examinations as hereinindicated, there is not the slightest difficulty in preparing a verylarge number of resins of various types and fro-m various reactants, andby means of different catalyst by different procedures, all of which areeminently suitable for the herein described purpose.

Now returning to the thought that cross-linking can take place, evenwhen difunctional phenols are used exclusively, attention is directed tothe following: Somewhere during the course of resin manufacture theremay be a potential crosslinking combination formed but actualcrosslinking may not take place until the subsequent stage is reached,i. e., heat and vacuum stage, or

or explained in terms of a, theory of flaws, or Lockerstellen, which isemployed in explaining flaw-forming groups due to the fact that a CHzOHradical and H atom may not lie in the same plane in the manufacture ofordinary phenol-aldehyde resins.

Secondly, the formation or absence of formation of insolublcs may berelated to the aldehyde used and the ratio of aldehyde, particularlyformaldehyde, insofar that a slight variation may, under circumstancesnot understandable, produce insolubilization. The formation of theinsoluble resin is apparently very sensitive to the quantity offormaldehyde employed and a slight increase in the proportion offormaldehyde may lead to the formation of insoluble gel lumps. The causeof insoluble resin formation is not clear, and nothing is known as tothe structure of these re ins.

All that has been said previously herein as regards resinification hasavoided the specific reference to'activity of a methylene hydrogen atom.Actually th re is a possibility that under some drastic conditionscross-linking may take place through formaldehyde addition to themethylene bridge, or some other reaction involving a methylene hydrogenatom. Finally, there is some evidence that, although the meta positionsare not ordinarily reactive, possibly at times methylol groups or thelike are formed at the meta positions; and if this were the case it maybe a suitable explanation of abnormal cross-linking.

Reactivity of a resin towards excess aldehyde, for instanceformaldehyde, is not to be taken as a criterion of rejection for use asa reactant. In other words, a phenol-aldehyde resin which isthermoplastic and solvent-soluble, particularly if xylene-soluble, isperfectly satisfactory even though retreatment with more aldehyde maychange its characteristics markedly in regard to, both fusibility andsolubility. Stated another way, as far as resins obtained fromdifunctional phenols are concerned, they may be eitherformaldehyde-resistant or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is tobe noted that they are thermoplastic phenol-aldehyde resins derived fromdifunctional phenols and are clearly distinguished from Novolaks orresoles. When these resins are produced from difunctional phenols andsome of the higher aliphatic aldehydes, such as acetaldehyde, theresultant is often a comparatively soft or pitchlike resin at ordinarytemperature. Such resins become comparatively fluid at 119 to 165 C. asa rule and thus can be readily oxyalkylated, preferably oxyethylated,without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily athermoplastic resin is identified as one which can be heated repeatedlyand still not lose its thermoplasticity. It is recognized, however, thatone may have a resin which is initially thermoplastic but on repeatedheatin may become insoluble in an organic solvent, or at least no longerthermoplastic, due to the fact that certain changes take place veryslowly. As far as the present invention is concerned, it is obvious thata resin to be suitable need only be sufiiciently fusible to permitprocessing to produce our oxyall zylated products and not yieldinsolubles or cause insolubilization or gel formation, or rubberiness,as previously described. Thus resins which are, strictly speaking,fusible but not necessarily thermoplastic in the most rigid sense thatsuch terminology would be applied to the mechanical properties of aresin, are useful intermediates. The bulk of all fusible resins of thekind herein described are thermoplastic.

'The fusible or thermoplastic resins, or solventsoluble resins, hereinemployed as reactants, are water-insoluble, or have no appreciablehydrophile properties. The hydrophile property is introduced byoxyalkylation. In the hereto appended claims and elsewhere theexpression water-insoluble is used to point out this characteristic ofthe resins used.

In the manufacture of compounds herein employed, particularly fordemulsification, it is obvious that the resins can be obtained by one ofa number or" procedures. In the first place, suitable resins aremarketed by a number of companies and can be purchased in the openmarket; in the second place, there are a wealth of examples of suitableresins described in the literature.

The third procedure is to follow the directions of the presentapplication.

The polyhydric reactants, i. e., the oxyalkylation-suscpetible,water-insoluble, organic solventsoluble, fusible, phenol-aldehyde resinsderived from difunctional phenols, used as intermediates to produce theproducts used in accordance with the invention, are exemplified byExamples Nos. la through 103a of our Patent 2,499,370, granted March 7,1950, and reference is made to that patcut for examples of theoxyalkylated resins used as intermediates.

Previous reference has been made to the use of a single phenol as hereinspecified, or a single reactive aldehyde, or a single oxyalkylatingagent. Obviously, mixtures of reactants may be employed, as for examplea mixture of parabutylphenol and para-amylphenol, or a mixture ofpara-butylphenol and para-hexylphenol, or para-butylphenol andpara-phenylphenol. It is extremely difficult to depict the structure ofa resin derived from a single phenol. When mixtures of phenols are used,even in equimolar proportions, the structure of the resin is even moreindeterminable. In other words, a mixture involving para-butylphenol andpara-amylphenol might have an alternation of the two nuclei or one mighthave a series of butylated nuclei and then a series of amylated nuclei.If a mixture of aldehydes is employed, for instance, acetaldehyde andbutyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde andacetaldehyde, the final structure of the resin becomes even morecomplicated and possibly depends on the relative reactivity of thealdehydes. For that matter, one might be producin simultaneously twodifferent resins, in what would actually be a mechanical mixture,although such mixture might exhibit some unique properties as comparedwith a mixture of the same two resins prepared separately. Similarly, ashas been suggested, one might use a combination of oxyalkylating agents;for instance, one might partially oxyalkylate with ethylene oxide andthen finish on with propylene oxide. It is understood that theoxyalkylated derivatives of such resins, derived from such plurality ofreactants, instead of being limited to a single reactant from each ofthe three classes, is contemplated and here included for the reason thatthey are obvious variants.

PART 2 Having obtained a suitable resin of the kind described, suchresin is subjected to treatment with a low molal reaction alpha-betaolefin oxide so as to render the product distinctly hydrophile in natureas indicated by the fact that it becomes amaooe the reactive ethyleneoxide ring and may be best considered as derivatives of or substitutedethylene oxides. The solubilizing effect of the oxide is directlyproportional to the percentage of oxygen present, or specifically, tothe oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is2:3; and in methyl glycide, 1:2. In such compounds, the ratio is veryfavorable to the production of hydrophile or surfaceactive properties.However, the ratio, in propylene oxide, is 1:3, and in butylene oxide,1:4. Obviously, such latter two reactants are satisfactorily employedonly where the resin composition is such as to make incorporation of thedesired property practical. In other cases, they may produce marginallysatisfactory derivatives, or even unsatisfactory derivatives. They areusable in conjunction with the three more favorable alkylene oxides inall cases. For instance, after one or several propylene oxide orbutylene ox de molecules have been attached to the resin molecule,oxyalkylation may be satisfactorily continued using the more favorablemembers of the class, to produce the desired hydrophile product. Usedalone, thesetwo reagents may in some cases fail to produce sufficientlyhydrophile derivatives because of their relatively low oxygen-carbonratios.

Thus, ethylen oxide is much more eifective than propylene oxide, andpropylene oxide is more effective than butylene oxide. Hydroxy propyleneoxide (glycide) is more effective than propylene oxide. Similarly,hydroxy butylene oxide (methyl glycide) is more eifective than butyleneoxide. Since ethylene oxide is the cheapest alkylene oxide available andis reactite, its use is definitely advantageous, and especially in lightof its high oxygen content. Propylene oxide is less reactive thanethylene oxide, and butylene oxide is definitely less reactive thanpropylene oxide. On the o .1 hand, glycide react with almost explosiveviolence and must be handled with extreme care.

The oxyalkylation of resins oi the kind from which the initial reac d. 5used in the practice of the present invention are prepared isadvantageously catalyzed by the presence of an alkali. Useful alkalinecatalysis include. soaps, sodium acetate, sodium hydroxide, sodiummethylate, caustic potash, etc. lhe amount of alkaline catalyst usuallyis between (1.2% to 2%. The temperature employed may vary'from roomtemperature to as high as 206 C. The reaction may-be conducted with orwithout pressure, i. e., from zero pressure to approximately 206 oreven. 3% pounds gauge pressur (pounds per square inch). In a generalway, the method employed is substantially the same procedure used foro-xyalkylation oi other organic materials having reactive phenolicgroups.

It'may be necessary to allow for the acidity of a resin in determiningthe amount of alkaline catalyst to be added in Oxyalkylation. Forinstance, if a nonvolatilestrong acid such as sulfuric acid sumablyafter being converted into a sulfonid acid, it may be necessary and isusually advantageous to add an amount of alkali equal stoichiometricallyto such acidity, and include added alkali over and above this amount asthe alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inertsolvent such as xylene, cymene, decalin, ethylene glycol diethylether,diethyleneglycol diethylether, or the like, although with many resins,the oxyalkylation proceeds satisfactorlly without a solvent. Sincexylene is cheap and may be permitted to be present in the final productused as a demulsifier, it is our preference to use xylene. This isparticularly true in the manufacture of products from low-stage resins,i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated,the pressure readings of course represent 'to'z-al pressure, that is,the combined pressure due to xylene and also due to ethylene oxide orwhatever other oxyalkylating agent is used. Under such circumstances itmay be necessary at times to use substantial pressures to obtaineffective results, for instance, pressures up to 300 pounds along withcorrespondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such asxylene can be eliminated in either one of tWo Ways: After theintroduction of approximately 2 or 3 moles of ethylene oxide,

for example, per phenolic nucleus, there is a definite drop in thehardness and melting point of the resin. At this stage, if xylene or asimilar solvent has been added, it can be elLminated by distillation(vacuum distillation if desired) .and the subsequent intermediate, beingcomparatively soft and solvent-iree, can be reacted further in the usualmanner with ethylene oxide'or some other suitable reactant.

Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

Another suitable procedure is to use propylene oxide or butylene oxideas a solvent as well as a reactantin the earlier stages along withethylene oxide,.'for instance, by dissolving the powdered resin in'propylene oxide even though oxyalkylation. is taking place to a greateror lesser degree. After a solution has been obtained which representsthe original resin dissolved in propylene oxide or butylene oxide, or amixture which includes the oxyalkylated product, ethylene oxide is addedto react with the liquid mass until hydrophile properties are obtained.Since ethylene oxide is more reactive than propylene oxide or butyleneoxide, the final product may contain some unreacted propylene oxide orbutylene oxide which can be eliminated by volatilization or distillationin ay suitable manner.

1 Attention is directed to the fact that the resins herein describedmust be fusible or soluble in an organic solvent. Fusible resinsinvariably are soluble in one or more organic solvents such as thosementioned elsewhere herein. It is to be emphasized, however, that theorganic solvent employed to indicate or assure that the resin meets thisrequirement need not be the one used in oxyalkylation. Indeed, solventswhich are susceptible to oxyalkylation are included in this group oforganic solvents. Examples of such solis used to catalyze thercsinification reaction, pre- 15 vents are alcohols and alcohol-others.However,

17 where a resin is; soluble in an organic solvent, there are usuallyavailable other organic solvents which arenot susceptible tooxyalkylation, useful for the oxyalkylation step. In any event, theorganic solvent-soluble resin can be finely powdered, for instance to100v to 200 mesh, and

a slurry or suspension prepared in xylene or the like, and subjected tooxyalkylation. Thefact that the resin is soluble in an organic solventorthe fact that it is fusible means that it consists of separatemolecules. of the type herein specified posse s reactive hydroxyl groupsand are oxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned withability to vary the hydrophile properties ofthe hydroxylatedintermediate reactants from minimum hydrophile properties to maximumhydrophile properties. Such properties in turn, of course, are effectedsubsequently by the acid employed for esterification and thequantitative nature of the esterification itself, i. e., whether it, istotal or partial, and also by the dimethylated higher aliphatic amineused to obtain. the final product for use in the process of the presentinvention. It may be well, however, to point out what has been saidelsewhere in regard to the hydroxylated intermediate reactants. See, forexample, our co-pending ap lications, Serial Nos. 8,730, and 8.731, bothfiled February 16, 1948, and Serial No. 42,133, filed August 2, 1948,and Serial No. 42,134, filed Augustv 2, 1948 (all four cases nowabandoned). The reason is that, the reactions. depending on the acid andthe, dimethylated higher aliphatic amine selected, may vary thehydrophile-hydrophobebalance in one direction or the other, and also.invariably causes the development of some property which makes it,inherently different from the, reactants from which the derivative isobtained.

Referring to the hydrophile hydroxylated intermediates, even more,remarkable and equally difficult to ex lain, are the versatility and theutility of these compounds cons dered as chemical reactants as one goesfrom minimum hydrophile property to ultimate maximum hydrophileproperty. For instance, minimum hydrophile property may be describedroughly as the po nt where two ethyleneoxy r dicals or moderately inexcess thereof are introduced per phenolic hydroxyl. Such minimumhydrophile property or sub-surface-activity or minimum surface-activitymeans that the product shows at. least emulsify-. ing properties orself-dispersion in cold or even in warm dist lled water to 40 C.) inconcentrations of 0.5% to. 5.0%. These materials are generally moresoluble in cold water than warm water, and may even be very insoluble inboiling Water. Moderately high temperatures aid in reducing the vscosity of the solute under ex-.. amination. Sometimes if one continuesto shake a hot solution, even though cloudy or containing an insolublephase, one finds that solution takes place to give a homogeneous phaseas the mix,- ture cools. Such self-dispersion. tests are conducted inthe absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2moles of ethylene oxide per phenolic nucleus or the equivalent) butinsufficient to give a. sol as described immediately preceding, then,and in that event hydrophile properties are ind cated by the fact thatone can produce an emulsion by having present 10% to 50% of an inertsolvent such as xylene. All that one need to do is to have a xylenesolu- Phenol-aldehyde resins.

ates-.095.

18 I tion within the range of 50 to parts by weight of oxyalkylatedderivatives and 50 to 10 parts by weight of xylene and mix such solutionwith one, two or three times its volume of distilled water and shakevigorously so as to obtain an emulsion which may be of the oil-in-watertype or the water-in-oil type (usually the former) but, in any event, isdue to the hydrophile-hydrophobe balance of the oxya-lkylatedderivative. We prefer simply to use the xylene diluted derivatives,which are described elsewhere, for this test rather than evaporate thesolvent and employ any more elaborate tests, if the solubility is notsuflicient to permit the simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethylor methyl alcohol, ethylene glycol diethylether, or diethylene glycoldiethylether, with a little acetone added if required, making a ratherconcentrated solution, for instance 40% to 50%, and then adding enoughof the concentrated alcoholic or equivalent solution to give thepreviously suggested 0.5% to 5.0% strength solution. If the product isself-dispersing (i. e., if the oxyalkylated product is a liquid or aliquid solution self-emulsifiable), such $01 or dispersion is referredto as at least semi-stable in the sense that sols, emulsions, ordispersions prepared are relatively stable, if they remain at least forsome period of time, for instance 30 minutes to two hours, beforeshowing any marked separation. Such tests are conducted at roomtemperature (22 C.) Needless to say, a test can be made in presence ofan insoluble solvent such as 5% to 15% of xylene, as noted in previousexamples. If such mixture, i. e., containing a water-insoluble solvent,is at least semi-stable, obviously the solvent-free product would beeven more so. Surface-activity representing an advancedhydrophile-hydrophobe balance can also be determined by the use ofconventional measurements hereinafter described. One outstandingcharacteristic property indicating surface-activity in a material is theability to form a permanent foam in dilute aqueous solution, forexample, less than 0.5%, when in the higher oxyalkylated stage, and toform an emulsion in the lower and intermediate stages of oXyalkylation.

Allowance must be made for the presence of a solvent in the finalproduct in relation to the hydrophile properties of the final product.The principle involved in the manufacture of the herein contemplatedcompounds for use as polyhydric reactants, is based on the conversion ofa hydrophobe or non-hydrophile compound or mixture of compounds intoproducts which are distinctly hydrophile, at least to the extent thatthey have emulsifying properties or are selfemuls fying; that is, whenshaken with water they produce stable or semi-stable suspensions, or, inthe presence of a water-insoluble solvent, such as xylene, an emulsion.In demulsification, it is sometimes preferable to use a product havingmarkedly enhanced hydrophile properties over and above the initial stageof self-emulsifiability, although we have found that with products ofthe type used herein, most eflicacious results are obtained withproducts which do not have hydrophile properties beyond the stage ofself-dispersibllity.

More highly oxyalkylated resins give colloidal solutions or sols whichshow typical properties comparable to ordinary surface-active agents.Such conventional surface-activity may be meas ured by determining thesurface tension and the 19 interfacial tension against paraflln oil orthe like. At the initial and lower stages of oxyal kylatlon,surface-activity is not suitably determined in this same manner but onemay employ an emulsification test. Emulsions come into existence as arule through the presence of a surface-active emulsifying agent. Somesurface-active emulsifying agents such as mahogany soap may produce awater-in-oil emulsion or an oilin-water emulsion depending upon theratio of the two phases, degree of agitation, concentration ofemulsifying agent, etc.

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylation, the so-calledsub-surface-active stage. The surface-active properties are readilydemonstrated by producing a xylene-water emulsion. A suitable procedureis as follows: The oxyalkylated resin is dissolved in an equal weight ofxylene. Such 50-50 solution is then mixed with l-3 volumes of water andshaken to produce an emulsion. The amount of xylene is invariablysufficient to reduce even a tacky resinous product to a solution whichis read'ly disp1rsible. The emulsions so produced are usuallyxylene-in-water emulsions (oil-in-water type) particularly when theamount of dist lled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At times,particularly in the lowest stage of oxyalkylation, one may obtain awaterin-xylene emulsion (water-in-oil type) which is apt to reverse onmore vigorous shaking and furs ther dilution with water.

If in doubt as to this property, comparison with a resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followed by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.Such resin prior to oxyalkylation has a molecular weight indicatingabout 4 units per resin molecule. Such resin, when diluted with an equalweight of Xylene, will serve to illustrate the above emulsificationtest.

In a few instances, the res n may not be sufficiently soluble in xylenealone but may require the addition of some ethylene glycol diethyletheras described elsewhere. It is understood that such mixture, or any othersimilar mixture, is considered the equivalent of xylene for the purposeof this test.

In many cases, there is no doubt as to the pres ence or absence ofhydrophile or surface-active characteristics in the polyhydric reactantsused in accordance with this invention. They dissolve or disperse inwater; and such dispersions foam readily. With borderline cases, i. e.,those which show only incipient hydrophile or surfaceactive property(sub-surface-activity) tests for emulsifying properties orself-dispersibility are.

useful. The fact that a reagent is capable of producing a dispersion inwater is proof that it is distinctly hydrophile. In doubtful cases,comparison can be made with the butylphenol-formaldehyde resin analogwherein 2 moles of ethylene oxide have been introduced for each phenolicnucleus.

The presence of xylene or an equivalent waterinsoluble solvent may maskthe point at which a solvent-free product on mere dilution in a testtube exhibits self-emulsification. For this reason, if it is desirableto determine the approximate point where self -emulsification begins,then it is better to eliminate the xylene or equivalent 20 from a. smallportion of the reaction mixture and test such portion. In some cases,such xylenefree resultant may show initial or incipient hydrophileproperties, whereas in presence of xylene such properties would not benoted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as xylene. It'is to be emphasized that hydrophileproperties herein referred to are such as those exhibited by incipientseif-emulsification or the presence of emulsifying properties and gothrough the range of homogeneous dispersibility or admixture with watereven in presence of added water-insoluble solvent and minor proportionsof common electrolytes as occur in oil field brines.

E1sewhere,it is pointed out that an emulsification test may be used todetermine ranges of surface-activity and that such emulsification testsemploy a xylene solution. Stated another way, it is really immateralwhether a xyene solution produces a sol or whether it merely produces anemulsion.

In light of what has been said previously in regard to the variation ofrange of hydrophile properties, and also in light of what has been saidas to the variation in the efiectfveness of various alkylene oxides, andmost particularly of all ethyene oxide, to introduce hydrophilecharacter, it becomes obvious that there is a wide variation in theamount of alkylene oxide employed, aslong as it is atleast 2 moles perphenolc nucleus, for producing products useful for the practice of thisinvention. Another variation is the molecular size or the resin chainresulting from reaction between the difunctional phenol and thealdehyde'such as formaldehyde. It is we'l known that the size and natureor structure of the resin polymer obtained varies somewhat withthecondtionsof reaction, the. proportions of reactants, the nature of thecatalyst, etc.

Based on molecular weight determinations, most of the resins prepared asherein described, particularly in the absence of a secondary heatingstep, contain 3 to 6 or '7 phenolic nuclei with approximately 4 or 5nuclei as an average.

More drastic conditions of resinfication yield.

resins of greater chain length. Such more intensive resinification is aconventional procedure and may be employed if desired.v Molecularweight, of course, is measuredby any suitable procedure, particularly bycryoscopic methods;

but us ng the same reactants and using morestance, an alkaline catalystis sometimes em,-

ployed in a first stage, followedby neutralization and addition of asmall amount of acid catalyst in a second stage. It is generallybelieved that even in the presence of an alkaline catalyst, the

number of moles of aldehyde, such as formaldehyde, must be greater thanthe moles of phenol employed in order to introduce methylol groups inthe intermediate stage. There is no indication that such groups appearin the final resin if prepared by the use of'an acid catalyst.' It ispossible that such groups may appear in the finished prepared byourselves. Our preference, however,

is, to use. an acid-catalyzed resin, particularly employing aformaldehyde-to-phenol ratio of 0.95 to;1.20 and, as far as;.we havebeen able todeterminep'i. such resins are free from methylol groups;amatter of'fact, it isprobable that in, acid-catalyzed:resini'fications, the methylol structure, may appear only momentarily atthe very beginning of the reaction and in all probability is convertedat once intoa more complex structure during the intermediate stage.

= 3 One procedure which can be employed in the use of a new resin toprepare polyhydric reactants for use in the preparationof compoundsemployed in ;the present invention, is to determine the hydroxyl value,by the Verley-Biilsing method or its equivalent. 7 The resin as, such,or in the'form ofj'a, solutionas described isthen treated with ethyleneoxide in. presence of 0.5% to 2% of sodium methylate as a catalystinstep-wise fashon. II'heconditions of, reaction, as far as time orpencent are concerned, are Within the range soft or pitch-like resin atordinar temperatures. such resins becom comparatively fluid at 110to-165i C. as a rule, and thus can be readily oxyalklated, preferablyoxyethylated, without the use of asolvent. I V

What has been said previously is not intended to suggest that anyexperimentation is necessary to determine the degree of oxyalkylation,and

particularly oxyethylation. What has been said previously, is submittedprimarily to emphasize the fact that these remarkable oxyalkylatedresins having surface activity show unusual properties as the hydrophilecharacter varies from a minimum "to an ultimate maximum. One should notunderestimate the utilit of any of these polyhydric alcohols in asurface-active or subsurfaceactive rangewithout examining them byreaction with a number of the typical acids and dimethylated higheraliphatic amines herein described and subsequently examining theresultant for utility, either in demulsi-fication or in some other artor industry as referred to elsewhere, or as a replicyiol'lslyindicated.With suitable agitation the thyleneoxide, it addedin molecularproportion, combineswithina comparatively short time, for instance .aflfe'wminutes to 2 .to 6 hours, but in some instances requires asmuchasS to 24 hours.

Afuscful temperaturerange is from'1-25? to 225 ,ufllhefcompletion of.vthe reaction or? each additionjf ethylne .oxide in step-wise fashionusuallylindicatedj bythe' reduction or elimination of, pressure; Anamount conveniently used for j each addition is generally equivalent toa molep f liwomolesof ethylene oxide per hydroxyl radical. Whenjithe.amount ofethylene oxide added is equ valent to approximately 50% byweight of the original resin, .a.'sample is testedfor incipienthydrophile, properties by simply shaking up in Watenasi is,,or.aftertheeliminatio n of thesolvent ifa solvent is present. .fI'heamount isethylene oxide used to obtaina .useful demulsifying agent as a rulevariesjrom 7.0% by Weight of the original resin to .as much as five orsix times the Weight of the original resin. In the case of a resinderived from para-tertiary butylphenol, as little as50 by weight ofethylene oxide "may give suitable solubility. With-pro? pylene oxide;'even'a greater molecular proper; tio'n is required and sometimes aresultantjof only limit'ed hydrophile properties is obtainable.

The" same is true td'even a greater extent with butylene "oxide. The"hydroxylated ,alxlene oxides are more effective in' solubilizingpropertiesthan the comparable compounds in which noihydroxyl is present.

,Attention' directed to the fact that in the subsequent examplesreference is made to the, stepwise additionof the alkylene aside-gush asethylene oxide. It understood, of course, there v is no-objiection' tothe continuous addition of alkyieneoxide. until the desired stage-ofreaction is reached. In? 'fact,1ther may-' b less of a haz ard ainvolvedand-it isoften advantageous to add the alkylene oxide slowly in acontinuous stream and. such. amountlas to avoid! exceeding the higher.pressureslnoted in the various examples or. elsewhere...

It may bewellto emphasize the fact that when resinsxare produced fromdifunctional phenols actant for the manufacture of more complicatedderivatives. A few simple laboratory tests which can be conducted inaroutine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having atleast three phenolic nuclei and. being organic solvent-soluble,Oxyethylate such resin, using the following four ratios of moles ofethylene oxide per phenolic unit equivalent: 2-to 1; 6' to 1; 10 to 1;and 15 to 1. From a sample of each product remove any solvent that maybe present such as xylene. Prepare 0.5% and 5.0% solutions in distilledwater, as previously indicated. A mere examination of such series willgenerally reveal an approximate range of minimum hydrophile character,moderate hydrophile character, and maximum hydrophile character. It the2 t0 ,1 ratio does not show minimum hydrophile character by test of thesolvent-free product, then one should test its capacity to form anemulsion when admixed with xylene or other insoluble solvent. If neithertest showsthe required minimum hydrophile property, repetition using 2/2 to 4 moles per phenolic nucleus will serve. Moderate hydrophilecharacter should be shown by either the 6 to 1 or 10 to 1 ratio. Suchmoderate hydrophile character is'indicated by the fact that the $01 indistilled water within the previously mentioned concentration range isapermanent translucent sol when viewed in a comparatively thin layer, forinstance the depth of a test tube. Ultimate hydrophile character isusually shown at the 15 to 1 ratio testin that adding a small amount ofan insoluble solvent, for instance 5% of xylene, yields a, product whichwill give, at least temporarily, a transparent or translucent sol of thekind just described. The formation of a permanent foam, when a 0.5%.1'9. 5.0% aqueous solution is shaken,

' is anexcellenttest for surface activity. Previous referenc has beenmade to the fact that otheroxyalkylating agents may require the use of'increased' amounts of alkylene oxide. Howeverpif one does not even; careto go to the troubleof calculating molecular weights one can usingapproximately 200% to 300% by Weight,

and some of the higher-aliphatic aldehydesfsuch;

as acetaldehyde, the resultant isa comparativelyf and a third exampleusing about 500% to 750% by weight, to explore the range ofhydrophilehydrophobe balance.

pacity of about to gallons as hereii'iafter described. Suchlaboratory-prepared routine compounds can then be tested for solubilityand, generally speaking, this is all that is required to ive a suitablevariety covering the hydrophile- U 'hydrophobe range. All these tests,as stated, are intended to be routine tests and nothing more. They areintended to teach a person, even though unskilled in oxyethylation oroxyalkylation,-how

tolprepare in a perfectly. arbitrary manner, a

series of compounds illustrating the hydrophilehydrophobe range. 1 I

If one purchases a thermoplastic or fusible resin on the open marketselected from a suit- "able number which are available, one might haveto make certain determinations in order tomake the quickest approach tothe appropriate oxyalkylation range. For instance, one should know (a)the molecular size, indicating the number of phenolic units; (b) thenature of the aldehydic residue, which is usually CH2; and (c) thenature of the substituent, which is usually butyl, amyl, or phenyl. Withsuch information one is. in substant ally the same posit on as if onehad per 'sonally made the resin prior to oxyethylation. For instance,the molecular weight of the. in.- ternal structural units of the resinof the follow-' ing over-simplified formula:

(n=1 to 13, or even more) is given approximately by the formula: (M01.wt. of phenol 2) plus mol. Wt. of methylene or substituted methyleneradical. The molecular weight of the resin would be n times the valuefor the internal limit plus the values for the terminal units. Theleft-hand terminal unit of the above structural formula, it will beseen, is identical with the recurring internal unit except that it hasone extra hydrogen. The right-hand terminal unit lacks the methylenebridge element. Using one internal unit of a resin as the basic element,a resins molecular weight is given approximately by taking (n plus 2)times the weight of the internal element. Where the resin molecule hasonly 3 phenolic nuclei as in the structure shown, this calculation willbe in errormby several per cent; but as it grows larger, to contain 6,9, or 12 phenolic nuclei, the formula comes to be more thansatisfactory.Using such an approximate weight, one need only introduce, for example,two molal weights of ethylene, oxide or product of minimal hydrophilecharacter.

from resins which are producing the quaternary ammonium compounds 24useful as intermediates for used in accordancewith the presentapplication, such examplesgiving exact'and complete details for carryingout the oxyalkylation procedure."

The resins, prior-to oxyalkylation; vary'from tacky, viscousiliquids tohard, 1 high-melting sol ids. Their ,color varies from 'alight yellowthrough amber, -to .a deep .red or even almost black. In the-manufactureof resins, particu-- larly hard resins, as the reaction-progresses theeaction mass frequently goes through -a liquid state to a sub-resinousor semi-resinous state, often characterized byi-being tacky or sticky,to a final complete resin; As the resin is subjected to oxyalkylationthese "same physical changes tend to take place in reverse. If onestarts with a solid resin, oxyalkylation tends to make it tacky orsemi-resinous and further oxyalkylation makes the tackiness disappearand changes the product to a liquid. Thus, as the resin is oxy'alkylatedit decr'eases'in viscosity, that is, becomes more liquid orchanges froma solid to a liquid, particularly when it is converted to thewater-dispersi ble or water-soluble stage. The color of the oxyalkylatedderivative is usually considerably light; er than the original productfrom which it is made, varying from a pale straw color to an aim:

her or reddish amber. The viscosity usuallyvar-i ies from that of anoil, like castor oil, to that'o'f a thick viscous sirup. Some productsare waxy.

Thepresence of a solvent, such as 15% xylene or the like, thins theviscosity considerably and ther oxyalkylation gives enhanced hydrophilecharacter. Although we have prepared and tested a large number ofoxyethylated products of the type described herein, we have found noinstance where the use of less than 2-moles of ethylene oxide perphenolic nucleus gave desirable products.

Examples lb through 1812, and the tables which appear in columns 51through '56 of our said Patent 2,499,370 illustrate oxyalkylationproducts also reduces the color in dilution. No undue significance needbe attached to the color for they reason that if the same compound isprepared in glass and in iron, the latter usually has somewhat darkercolor. If the resins are prepared as customarily employed in varnishresin manufacture, i. e.' aprocedure that excludes the presence ofoxygen during the re inifica'tion and subsequent cooling of the resin,then of course the initial resinis much lighter incolor. We haveemployed some resins which initially are almost water-White and alsoyield a lighter colored final; product. r q Actually. in considering theratio of alkylene-' oxide to add, and we have previously pointed;outthatthis can be predetermined using laboratory tests, it is our actralpreference from a practical-- standpoint to ,make tests on asmall pilotplant scale. Our reason for so doing is that we make one run, and onlyone, a n d that we have a-complete series which shows the-progressiveeffect of introducing the oxyalkylating agent, for instance, theethyleneoxy radicals. Our preferred 'proced'a ure is .as follows: Weprepare a suitable resin, or

for that matter, purchase it intheopen'market; We employ 8 pounds ofresin and 4 pounds ofxy lene and place the resin and Xylene in suitableautoclave with an open reflux condenser. We prefer to heat and stiruntil the solution is complete.

'We have pointed out that soft resins which arefluid or semi-fluid canbe readily. prepared in variv ous ways, such as the use ofortho-tertiary amylphenol, ortho-hydroxydiphenyl, orthoedecylphe- J nol,or by the use of higher molecular weight aldehydes than formaldehyde. Ifsuch resinsare used,

a solvent'need not be added but may be added as a matter of convenienceor for comparison, if desired. We then add a catalyst, for instance, 2%

. 25 l usethe equipment as an autoclave only, and oxyethylate until atotal of 60 pounds of ethylene oxide have been added, equivalent to 750%of the original resin. We prefer a temperature ,of about 150 C. to 175C. We also take samples at intermediate points as indicated in thefollowing table:

Pounds of Ethylene Percentages Oxide Added per 8-pound Batch lution maybe suflicient to indicate hydrophile character or surface activity, i.e., the product is soluble, forming a colloidal sol, or the aqueoussolution foams or shows emulsifying property. All these properties arerelated through adsorption at the interface, for example, a gas-liquidinterface or a liquid-liquid interface. If desired, surface activity canbe measured in any one of the usual ways using a Du Nouy tensiometer ordropping pipette, or any other procedure for measuring interfacialtension. Such tests are conventional and require no furtherdescription.- Any compound having sub-surface-activity, and all derivedfrom the same resin and oxyalkylated to a greater extent, i. e., thosehaving a'greater proportion of alkylene oxide, are useful as polyhydricreactants for the practice of this invention,

Another reason why we prefer to use a pilot planttest of the kind abovedescribed is that we can use the same procedure to evaluate tolerancetowards a trifunctional phenol such as hydr0xy-" benzene or metacresolsatisfactorily. Previous reference has been made to the fact that onecan conduct a laboratory scale test which will indicate whether or not aresin, although soluble in solvent, will, yield an insoluble rubberyproduct, i. e., a product which is neither hydrophile nor surfaceactive,upon oxyethylation, particularly extensive oxyethylatiomf It is alsoobvious that one may have a solvent-soluble resin derived from a mix-'-ture of phenols having present 1% or 2% of a trifunctional phenol whichwill result in an insoluble rubber at the ultimate stages ofoxyethylation but not in the earlier stages. In other words, with resinsfrom some such phenols, addition of-2 or 3 moles of the oxyalkylatingagent per phenolic nucleus, particularly ethylene oxide, gives asurface-active reactant which is perfectly. sati'sfac tory, while moreextensive oxyethylation yields an ating trifunctional phenol toleranceis more suitable than the previous procedure.

It may be well to call attention to one result which may be noted in along drawn-out oxyalkylation, particularly oxyethylation, which wouldnot-appear in a normally conducted reaction. Reference'has been made tocross-linking and its eifect on solubility and also the fact that,ifcarried far enough, it causes incipient stringiness, then pronouncedstringiness, usually followed by a. semi-rubbery or. rubbery stage.Incipient stringiness, .or even pronounced stringiness, or even thetendency towarda rubbery stage, is not objectionable so long as thefinal product is still hydrophile and at least sub-surface-active. Suchmaterial frequently is best mixed with a polar solvent, such as alcoholor the like, and preferably an alcoholic solution is used. The pointwhich'we want to make here,- however, is this: Stringiness orrubberization at this stage may possiblybe the result-of etherification.Obviously if a difunctional phenol and an aldehyde produce anon-cross-linked resin molecule and if such molecule is oxyalkylated soas to introduce a plurality of hydroxyl groups in each molecule, thenand in that event if subsequent etherification takes place, one is goingto obtain crosslinking in the same general way that one would obtaincross-linking'in other resinification reactions; Ordinarily there islittle or no tendency toward etherification during" the oxyalkylationstep, If "it does take place at all, it is only to an insignificant andundetectable degree. However, suppose that a certain weight of resin istreated with an equal weight of, or twice its weight of; ethylene oxide.This may be done in a comparatively short time, for instance, at or C.in 4 to 8 hours, or even less. On the other hand, if in an exploratoryreaction, such as the kind previously described, the ethylene oxide wereadded extremely slowly in order to take stepwise samples, so that thereaction required 4 or'5 times as long to introduce an equal amount ofethylene oxide employing the same temperature, then etherification mightcause stringines's' or a suggestion of rubberiness. For this reason ifin an exploratory experiment of the kind previously described thereappears to be any stringiness or rubberiness, it may be well to repeatthe experiment and reach the intermediate stage of oxyalkylation asrapidly as possible and then proceed slowly beyond this intermediatestage. The entire purpose of this modified procedure is to cut down thetime of reaction so as to avoid etherification if it be caused by theextended time period.

It may be well to note-one peculiar reaction sometimes noted in thecourse of oxyalkyiation, particularly oxyethylation, of thethermoplastic resins herein described. This effect is noted in a casewhere a thermoplastic resin has been oxyalkylated, for instance,oxyethylated, until it gives a perfectly clear solution, even in thepresencepf some accompanying water-insoluble sol vent such as 10% to'15%of xylene. Further oxyalkylation, particularly oxyethylation, may thenyielda product which, instead of giving a clear solution as previously,gives a very milky solution suggesting that some marked change hasjtakenplace. One explanation of the above change is that the structural unitindicated in ,theyfolloWing way where 8n'is a fairly large number, forinstance, 10 to 20, decomposes and an oxyalkylatecl resin representing alower degree of oxyethylation and a less soluble one, is generated and acyclic polymer of ethylene oxide is produced, indicated thus:

This fact, of course, presents no dimculty for the reason thatoxyalkylation can be conducted in each instance stepwise, or at agradual rate, and samples taken at short intervals so as to arrive at apoint where optimum surface activity or hydrophile character is obtainedif desired; for products for use as polyhydric reactants in the practiceof this invention, this is not necessary and, in fact, may beundesirable, i.-e., reduce the efliciency of the product.

We do not know to what exent oxyalkylation produces uniform distributionin regard to phenolic hydroxyls present in the resin molecule. In someinstances, of course, such distribution can not be uniform for thereason that we have not specified that the molecules of ethylene oxide,for example, be added in multiples of the units present in the resinmolecule. This may be illustrated in the following manner:

Suppose the resin happens to have five phenolic nuclei. If a minimum oftwo moles of ethy.ene oxide per phenolic nucleus are added, this wouldmean an addition of moles of ethylene oxide, but suppose that one added11 moles of ethylene oxide, or 12, or 13, or 14 moles; obviously, evenassuming the most uniform distribution possible, some of thepolyethyleneoxy radicals would containB ethyleneoxy units and some wouldcontain 2. Therefore, it is impossible to specify uniform distributionin regard to the entrance of the ethylene oxide or other oxyalkylatingagent. For that matter, if one were to introduce 25 moles of ethyleneoxide there is no way to be certain that all chains of ethyleneoxy unitswould have 5 units; there might be some having, for

example, 4 and 6 units, or for that matter 3 or 7' units. Nor is thereany basis for assuming that the number of molecules of the oxyalkylatingagent added to each of the molecules of the resin is the same, ordifferent. Thus, where formulae are given to illustrate or depict theoxyalkylated products, distributions of radicals indicated are to bestatistically taken. We have, however, included specific directions andspecifications in regard to the total amount of ethylene oxide, or totalamount of any other oxyalkylating agent, to add.

In regard to solubility of the resins and the oxyalkylated compounds,and for that matter derivatives of the latter, the following should benoted. In oxyalkylation, any solvent employed should be non-reactive tothe alkylene oxide employed. This limitation does not apply to solventsused in cryoscopic determinations for ob vious reasons. Attenton isdirected to the fact that various organic solvents may be employed toverify that the resin is organic solvent-soluble. Such solubility testsmerely characterizes the resin. The particular solvent used in such testmay not be suitable for a molecular weight determination and, likewise,the solvent used in determining molecular weight may not be suitable asa solvent during oxyalkylation. For solu- O H Ommmomn Gownnomn vtiori ofthe oxyalkylated compounds, or their de-- rivatives a great variety'of'solvents may be employed, such as alcohols, ether alcohols,CIGSOlSy;

Reference to cryoscopic measurement is concerned with the use of benzeneor other suitable compound as a solvent. Such method will show thatconventional resins obtained, for example, from para-tertiary amylphenoland formaldehyde in presence of an acid catalyst, will have a molecularweight indicating 3, 4, 5 or somewhat greater number of structural unitsper molecule. If more drastic conditions of resinification are employedor if such low-stage resin is subjected to a vacuum distillationtreatment as previously described, one obtains a resin of a distinctlyhigher molecular weight. Any molecular weight I determination used,whether cryoscopic measurement or otherwise, other than the conventionalcryoscopic one employing benzene, should bechecked so as to insure thatit gives consistent values on. such conventional resins as. a control.make an approximation of the molecular weight range is to make acomparison with the dimer obtained by chemical combination of two moles"of 'the same phenol and one mole of the same aldehyde under conditionsto insure dimerization. Asto the preparation offsuch dimers fromsubstituted phenols, isee Carswell, Phenoplasts, page31." The increasedviscosity, resinous character, and decreased solubility, etc., of thehigher polymers in comparison with the dimer, frequently areall that isrequired to establish that the resin contains 3 or more structural unitsper molecule.

Ordinarily the oxyalkylation is carried out in autoclaves provided withagitators or stirring devices. We have foundthat the speed of theagitation markedly influences the reaction time. In some cases, thechange from slow speed agitation, for example, in a laboratory autoclaveagitation with a stirrer operating at a speed of 60 to 200 R. P. M., tohighspeed agitation, with the stirrer operating at 250 to 350 R. P.M.,'re-

' duces' the time required foroxyalkylation by when produced by similarprocedure'but 'with' high speedagitation, as "a'result, we'believe, of

the .reduction'inthe time required with conse-' quent elimination orcurtailment of opportunity Frequently all that is necessary to" 29 forcuring or etherization. Even if ,theformation of an insoluble product isnot involved, it is frequently advantageous to speed up the reaction,thereby reducing production time, by increasing agitating speed. Inlarge scale opera.- tions, we have demonstrated that economicalmanufacturing results from continuous oxyalkylation, that is, anoperation in which the alkylene oxide is continuously fed to thereaction vessel, with high speed agitation, i. e., an agitator operatingat 250 to 350 R. P. M. Continuous oxyalkylation, other conditions beingthe same, is more rapid than batch oxyalkylation, but the latter isordinarily more convenient for laboratory operation. 7

Previous reference has been made to the fact that in preparing compoundsof the kind herein described, particularly adapted for demulsificationof water-in-oil emulsions, and for that matter for other purposes, oneshould make a complete exploration of the wide variation inhydrophobe-hydrophile balance as previously referred to. It has beenstated, furthermore, that this hydrophobe-hydrophile balance of theoxyalkylated resins is imparted, as far as the range of variation goes,to a greater or lesser extent to the herein described derivatives. Thismeans that one employing the present invention should take the choice ofthe 'most suitable derivative selected from a number of representativecompounds, thus, not only should a variety of resins be preparedexhibiting a variety of oxyalkylations, particularly oxyethylations, butalso a variety of derivatives. This can be done conveniently in light ofwhat has been said previously.

From a practical standpoint, using pilot plant equipment, for instance,an autoclave having a capacity of approximately three to five gallons.We have made a single run by appropriate selections in which the molalratio of resin equivalent to ethylene oxide is one to one, 1 to 5, l to10, 1 to 15, and 1 to 20. Furthermore, in making these particular runswe have used continuous addition of ethylene oxide. In the continuousaddition of ethylene oxide we have employed either a cylinder ofethylene oxide without added nitrogen, provided that the pressure of theethylene oxide was sufficiently great to pass into the autoclave, or

else we have used an arrangement which, in essence, was the equivalentof an ethylen oxide cylinder with a means for injecting nitrogen so asto force out the ethylene oxide in the manner of an ordinary seltzerbottle, combined with the means for either weighing the cylinder ormeasuring the ethylene oxide used volumetrically." Such procedure andarrangement for injecting liquids is, of course, conventional. Thefollowing .data sheets exemplify such operations, i. e., the combinationof both continuous agitation and taking samples so as to give fivedifferent variants in oxyethylation. In adding ethylene oxidecontinuously, there is one precaution which must be taken at all times.The addition of ethylene oxide must stop immediately if there is anyindication that reaction is stopped or, obviously if reaction is notstarted at the beginning of the reaction period. Since theaddition ofethylene oxide is invariably an exothermic reaction, whether or notreaction has taken place can be judged in the usual manner by observing(a) temperature rise or drop, if any, (b) amount of cool ing water orother means required to dissipate heat of reaction; thus, if there is atemperature drop without the use of cooling water or equivalent, or ifthere is no rise in temperature without using cooling water control,careful investigation should be made.

In the tables immediately following, we are showing the maximumtemperature which is usually the operating temperature. In other words,by experience We have found that if the initial reactants are raised tothe indicated temperature and then if ethylene oxide is added slowly,this temperature is maintained by cooling water until the oxyethylationis complete. We have also indicated the maximum pressure that weobtained or the'pressure'range." Likewise, we'have indicated the timerequired to inject the ethylene oxide as well as a brief note as to thesolubility of the product at the end of the oxyethylation period. As oneperiodends it will be noted we have removed part of the oxyethylatedmass to give us derivatives, as therein described; the rest has beensubjected to further treatment. All this is apparent by examining thecolumns headed Starting mix, Mix at end of reaction, Mix which isremoved for sample, and Mix which remains as next starter.

The resins employed are prepared in the mannerdescribed in Examples 1athrough 103a of our said Patent 2,499,370, except that instead of beingprepared on a laboratory scale they were prepared in 10 to l5-gallonelectro-vapor heated synthetic resin pilot plant reactors, asmanufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, andcompletely described in their Bulletin No. 2087 issued in 1947, withspecific reference to Specification No. 7l3965.

For convenience, the following tables give the numbers of the examplesof our said Patent 2,499,370 in which the preparation of identicalresins on laboratory scale are described. It is understood that in thefollowing examples, the change is one with respect to the size of theoperation.

The solvent used in each instance was xylene. This solvent isparticularly satisfactory for the reason that it can be removed readilyby distillation or vacuum distillation. In these continuous experimentsthe speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if acomparatively small sample is taken at each stage, for instance, to onegallon, one can proceed through the entire molal stage of l to 1, to lto 20, without remaking at any intermediate stage. This is illustratedby Example 10%. In other examples we found it desirable to take a largersample, for instance, a 3-gallon sample, at an intermediate stage. As aresult it was necessary in such instances to start with a new resinsample in order to prepare suflicient oxyethylated derivativesillustrating the latter stages. Under such circumstances, of course, theearlier stages which had been previously prepared were by-passed orignored. This is illustrated in the tables Where, obviously, it showsthat the starting mix was not removed from a previous sample.

Phenol for resin: Para-tertiary amylphenol Aldehyde for resin:Formaldehyde Date, June 22, 1948 v [Resin made in pilot plant sizebatch, approximately pounds, corresponding to 3a of Patent 2,499,370 butthis batch designated 1040.]

- Mix Which is Mix Which Restarting Mix at of Removed for mains as Nexteac 0 Sample Starter Max. Max. Time Pressure Temperahrs Solubility 7lbs. sq. in. ture, C. lbis. gbs. Lbs kbs. Lbs abs. Lbs abs. Lbs 0 esoeso eso esvent in Eto vent in Eto vent in vent in Eto First Stage Resinto EtO. Molal Ratio 1:1 14. 25 15. 75 0 14. 25 15. 75 4. 0 3. 3. 1. 010. 9 12. 1 3. 0 80 150 $4 I Ex. No. 104b Second Stage Resin to EtO vMolal Ratio 1:5. 10 9 12. 1 3. 0 10. 9 12. 1 15. 25 3. 77 4. 17 5. 31 7.13 7. 93 9. 94 158 l ST Ex. No. 105b 1 Third Stage Resin to Et0. MolalRatio 1:10 7 13 7. 93 9. 94 7. 13 7. 93 19. 69 3. 29 3. 68 9. 04 3. 844. 25 10. 65 60 173 55 PS EX. No. 106b Fourth Stage Resin to EtO MolalRatio 1:15- 3 84 4. 25 10. 65 3. 84 4. 25 16. 15 2. 04 2. 21 8. 55 1. 2.04 7. 60 220 160 16 RS Ex. No. 107D.

Fifth Stage Resin to EtO. Molal Ratio 1:20- 1 80 2. 04 7. 60 1. 80 2. 0410. 2 Ma QS Ex. No. 108b.

I=Insoluble. ST=Slight tendency toward becoming soluble. FS=Fairlysoluble. RS=Readily soluble. QS=Quite soluble.

Phenol for resin: Nonylphenol Aldehyde for resin: Formaldehyde Date,June 18, 1948 [Resin made in pilot plant size batch, approximately 25pounds, corresponding to 70a of Patent 2,499.370 but this batchdesignated 10911.]

. Mix Which is Mix Which Re- Starting Mix fi 3 3 2 33 or Removed formains as Next Sample Starter Max Max 1tljressu e 'iemp egx- 1 2Solubility Lbs. Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs Lbs Lbs. Lbs Lbs Sol-Res- Sol- Res- Sol- Res Sol- Resvent in Eto vent in ELO vent in Eto ventin Eto First Stage Resin to EtO Molal Ratio 1:1 15 0 15.0 0 15.0 15.0 35.0 5.0 1.0 10.0 10.0 2.0 50 150 1% ST Ex. No. 109l) Second Stage Resinto Et0 Molal Ratio 1:5 10 10 2. 0 10 10 9. 4 2. 72 2. 72 2. 56 7. 27 7.27 6.86 100 147 2 DT Ex. No. 1l0b Third Stage Resin to EtO I Molal Ratio1:10. 7 27 7. 27 0. 86 7. 27 7. 27 13. 7 4. 16 4. 16 7.68 3. 15 3. 15 5.95 125 1% S Ex. N0. 1110.--" V Fourth Stage Resin to EtO Molal Ratio1:15. 3 15 3.15 5. 95 3. 15 3.15 8.95 1.05 1.05 2.95 2.10 2.10 6.00 220174 2% S Ex. No. 112b Fifth Stage Resin to EtO. 1 Molal Ratio 1:20. 2 102. 10 6.00 2. 10 2.10 8. 00 v 220 183 34; VS EX.No.113b

S=Soluble. ST =Slight tendency toward solubility. DT=Deflnite tendencytoward solubility. VS=Vei y soluble.

. 1 j 1Phenolforgresin: Para-octylphen-ol Date, June 23, 24, 1948 [Resinmade inpiiot plant size batch, approximately pounds, corresponding to Soof Patent 2,499,370 but this batch designated 1140.]

Aldehyde for resin: Formaldehyde Mix Which is Mix Which Restarting Mixfig figg of Removed for mains as Next Sample Starter Max Max TimePressure Tempsrahrs Solubility gbls. abs. Lbs gbls. Ifibs. Lbs r b s. Ibs. Lbs l b s. Ifibs. Lbs

o eso eso eso esvent in Eto vent in Eto vent in Eto vent in Eto FirstStage Resin to Et0 Moiai Ratio 14.2 15.8 0 14.2 15.8 3.25 3.1 3.4 0.7511.1 12.4 2.6 150 1342 NS Ex. No. 114b.

Second Stage Resin to EtO. Molal Ratio 15... 11.1 12.4 2.5 11.1 12.412.5 7.0 7.82 7.88 4.1 4. 58 4.62 171 )6 SS Ex. No. 5b

Third Stage Resin to EtO Molal, Ratio 1:10. 6.64 7.36 0 6.64 7.36 15.0190 1% 8 Ex. No. 116b.

Fourth Stage Resin to 13110.... M0121 Ratio 1:15. 4.40 4.9 0 4.4 4.914.8 400 160 )4 VS Ex. No. 117b.

Fifth Stage Resin to Et O Molai Ratio 1; 20. 4.1 4.58 4.62 4.1 4.5a13.52 260 172 $4. vs Ex. No. 118b S=So1uble. NS=Not soluble. SS =Somew1at soluble. VS=Very soluble.

Plieml'fe aresi en y p 7 Date, July 8-13, 1948 [Resin made in pilotpiant size pat'chfapproxiniately 25 pounds, corresponding to 69a ofPatent 2,499,370 but this batch designated 119a.]

Aldehyde for resin: Formaldehyde Mix Which is Mix Which Restarting Mixfigg ggg of Removed for mains as Next Sample Starter Max. Max. Time vPressure 'lempgrahrs Solubility Lbs. Lbs. Lbs; Lbs. Lbs. Lbs. Lbs. Lbs.Sol- Res- Res- Sol- Res-, Sol- Res- 1 .....ym. .Y e in First Stage Resinto EtO.

Moial Ratio 1:1 13.65 16.35 0 13 65 16.35 3.0 9.55 11.45 2.1 4. 1 4.90.9 60 150 156 NS Ex. No. 119b Second Stage Resin to EtO"-. i 3 MolalRatio 10 12 0 12 10.75 4.52 5.42 4.81 5.48 6. 58 5.94 160 1952 8 Ex. No.1200--- Third Stage 1 Resin to Et0 g I Molal Ratio 1:10. 5.48 6. 58 5.945.48 6. 58 10.85 90 160 H 5 Ex. No. 121b- Fourth. Stage Resinto-EtOMolal Ratio 1:15 4. 1 4.9 0. 9 4. 9 13.15 180 171 1542 VS Ex. No.1220..." Fifth Stage Molal Ratio 1:20- 3.10 3. 72 0.68 3.10 3.72 13.43320 VS Ex. No. 123b S-Soluble. NS-Not soluble. VS=Very soluble.

Phenolfof resin: Para-secondury butylphenpl" A ld'efiyde'fbrresih:Fbrmaldehyde Date, July 14-15, 1948 [Resin made in pilot plant sizebatch. approximately 25-pounds; correspondingte2iroivPatenii2449937013115thisbatch designated 12411.]

- 3 Mix Whiehis 1- Mix Which Re- Starting Mix g figg RemovedTor mainsas.Next

6 Sample Starter Max Max Time nlj'ressuge fimpgighrs Solubility's.sq..n. e ei- .1221 .2:ezzu e ;ase ee-ezae vent in vent in v vent invent in:

First Stage Resinto F120-.-" I r Molai Ratio 1 14; 15. 0 14. 45 15.55 4.25 5.97 6. 38 1. 8. 48 9. 17 2.50 60 150* 5f: NB Ex. N0. 124!) SecondStage Resin m EtO I Molal-Ratio 1:5..- 8548 9.17 2.50 8.48 9.17 16.0" 5.83 6. 32 11.05 2.65 2.85 4.95 95 188' M SE Ex. N 0. 125b V 1 Third Stage1 Resin to EtO a Molal Ratio 1:10. 4.82 5.18 0 4. 82 5:18- l4-.25 4001831 $6 S Ex. N0. 12Gb Fourth Stage I Resin to EtO v V I Molal Ratio1:15- 3. 85 4.15 0 3.?85 4.15 17.0" 120 180 $6 V5 Ex. No. 12712---. I

Fifth Stage l Resin to EtO Molal Ratio 1:20 2.65 2. 85 4.95 2.65" 2. 8515.45 80 7 170 fi VS Ex. No. 128b I S=So1ub1e. NS=Not soluble.SS=Somewhat soluble. VS'=Very-so1ub1e:

Date, August 12-13, 1948 Phenolfor resih: Men-thyl' Aldefiyctfbr resin:Piopionaldefiyd [Resin made. on pilot plant size batch, approximately 25pounds, corresponding 170 81a ofjPatent 2,499,370 but this batchdesignated 12911.]

. Mix Which is Mix Which Re- Starting Mix if 'g figg Removed Iormains'as N ext 7 Sample Starter. Mam M-ax I Pressure Tempera- Solubility lbssq in tine "0 gbs. Lbs kbs. Lbs gbs. Lbs, Ifibs. I 0- es- 0- es- 1 0--es- 0-- es-"- vent in Eto vent in vent; in E vent. in fl First StageResin to E110"... Molal Ratio :1 12.8 17.2. 2.75 4. 25 517 0: 8555 11.50 12 80 150i 3% Not soluble. Ex.N0.129b I v i i 2.

Second Stage Resin to E--- f Molal Ratio 1:5 8.55 11.50 1.80 8.55 11. 509.3 4.78. 6.42. 522 3177 5508 4: 10 x 100 170 Somewhat Ex.N0.130bsoluble:

Third Stage Resin to EtO Molai Ratio 1:10- 3. 77 5. 08 4. 10 3. 77 5. 0813. 1 100. 182i M a 801111316: Ex. No. 1310------ Fourth Stage Resin toE tO V Molal Ratio 1:l5 5.2 7.0. 5.2 7.0 17.0 3.10 4.17 10.13 2.10.2.83. 6. 87 200 182 Y 34- Verysolirble. Ex:N0. 132b Y 1 r- A Fifth StageResin to EtO V Molal Ratio 1:20 2.10 2.83 6.87 2.10 2.83 9.12 90 iVerysoluble. Ex. No. 1330:..... i i j Phenol for resin: Para-tertiaryamylphenol Date, August 27-31, 1948 [Resin made on pilot plant sizebatch, approximately pounds, corresponding to 42a of Patent 2.499.370but this batch designated as 13411.]

Aldehyde for resin: Furfural Mix Which is Mix Which Re- Starting Mix gggg of Removed for mains as Next Sample Starter Max Max PressureTempgera- 3,2 Solubility Lbs. Lbs. Lbs. Lbs. Lbs Lbs. Lbs. Lbs Lbs. Lbs.mm Sol- Resb' Sol- Res- Sol- Res- Sol- Resb' vent in vent in vent invent in First Stage Resin to Eton--- Molal Ratio 1:1-.- 11.2 18.0 11.218.0 3.5 2.75 4.4 0.85 8.45 13.6 2.65 120 135 Not soluble. Ex. No.1340------ Second Stage Resin to EtO Mola1Ratio1:5-- 84513.6 2.65 8.4513.6 12.65 5.03 8.12 7.55 3.42 5.48 5.10 150 )4 Somewhat Ex. N 0. 135bsoluble.

Third Stage Resin to EtO.. Molal Ratio1:10-- 4.5 8.0 4.5 8.0 14.5 2.454.35 7.99 2.05 3.65 6.60 180 163 V1 Soluble. Ex.No.136b

Fourth Stage Resin to EtO MolalRatio1:15- 3.42 5.48 5.10 3.42 5.48 15.10180 188 so Verysoluble. Ex. Nov 137b Fifth Stage Resin to EtOMolalRati01:20 2.05 3.65 6.60 2.05 3.651335 $5 Verysoluble. Ex.N0.138b

Date, Sept. 23-24. 1948 Phenol for resin: Menthyl Aldehyde for resin.Furfural [Resin made on pilot size batch, approximately 25 pounds,corresponding to 89a of Patent 2,499,370 but this batch designated as13911.]

. Mix Which is Mix Which Re- Starting Mix fi g figg of Removed for mainsas Next Sample Starter Max. Max. Time 1tli'ressure 'emp ege- Solubility5. sq. m. ure, 52%: 22: ggg sBf: 322: 5 s: 23: s'lif: 322: $3 vent invent in vent in vent in First Stage Resin to EtO. MoialRatioLL- 10.2517.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 90 46 Not soluble.Ex No. 13911 Second Stage Resin to EtO. MolalRatio1:5.-- 7.6 13.15 1.857.6 13.15 9.35 5.2 9.00 6.40 2.4 4.15 2.95 80 177 Somewhat :Ex.No.140bsoluble.

Third Stage Resin to EtO.--" Molal Ratio 1:10 4.22 6.98 4.22 6.98 10.090 16:. 44 Soluble. Ex.No.141b

Fourth Stage Resin to 'EtO-.- Mo1alRatio1:15 3.76 6.24 3.76 6.24 13.25100 171 94 Verysoluble. Ex. No.142b

Fifth Stage Resin to EtO Mola1Rati01:20 2.4 4.15 2.95 2.4 4.15 11.70 90150 $4 Verysoluble Ex. No.143b--- Resin to EtO [Resin made on pilotplant size batcl1, appr0ximate1y pounds,porres ponding to 420 of Patent2,499 370 wit 206 parts by weight of commercial =1 1 Mix whihis' Mixwm hRe- Starting Mix 12011151701101" 1 11121115 5511510 E Sample Starter Max Max 1 I Time I lgresssure' '{emgeaahrs Solubility w 1. s-. q.in. ure'Lbs. Lbs. Lbs Lbs. .Lps. L, lib-S: L135. g Sol- Res- Eto Soi- Res- Etc301- 1 vent in vent in in 'vent m First Stage:

11 51110012001... v MolaLL-Ratid 1:1" 12:1 18. 6 12. 1' I18. 6' 3.0 i 5.38 8. 28 i 1.34 6. 72 10.32 7 1: 66 80 150 M2 :Insolubiec- Ex. No.1440..-

Second Stage i t; m9- Resin to E00 U p M r j e n c y' 00; MblaLRatid 1:59.125 14. 25 2..-... 9.25 14. 25 11.0 1 3. 73 5 5.73 4.44 5. 52 83526556 100 177 912' $75101 be- Ex. N0.- 1450... coming soluble. ThirdStage 5 5 Y Resin m 1310;". MolalSRatifi 1:10. 16.72 10.32 1.66 6. 72'10. 32 14. 91 I 1. 97 r 7. 62 11.01 a 1.75 2; 5 3.90 '5 85 182 1 M IFairly s0]!!- Ex. No. 14Gb l ble:

Fourth Stape Resin to EtOI 1 f V Molzih-Ratib' 1:15 55:52 8.52 6. 56 5.52 8. 52 19. 81 2 1 100 '1 176 'Readily SD1- Ex. No. 14712;... ub

Fifth Stagk Resinto EtOI... Iv'ipiPBatiD 1:20. 12 2.70 3.90 1.75 2.708.4 I 160 $4 Quite Soil!- Ex. N0. 148b bl;

Phenol for resin: Para-phenyl Aldehyde for resin: Furfur'al Date;October 11-13, 1948 [Resin'madeon pilot'plant'size'batch; approximate]wfipoundsycorrespondipgto 4200f Patent2;499,37(1 with170'p'arts byweight"ot'con1mercial para'phenyiphenol replacing 164'parts by weight ofpara-ternary amylphenol but this batch designated as 14911.]

Mum End'of Mix W1ii011is" Mix Which Re- S'tartin'Mix: ReaemmRersrgggllifor' maiisigfigext' b r i ax.'=; Tem era- Solubility m .1hrs. 1 1 v 5 1bs.sq. in. ture C.

vent in vent in 1 vent in 1 vent First Stade 11 10101110110 13.9 10.713.0 10.? 3.0 3.50 4325 0.80 10.35 12.45 2.20 100 Ex. No. 149b i SecondStdge I Re's'ifitEtO v A I} k M0121 Ratio 10.35 12. 45 2.20 10.35 12.4512.20 5.15 0.19 0.00 5.20 0:20 0.14 so 153 25 .watgsolu- Ex. N0. 150b.bility';

Third Stage V V V E J 7 3; Resin to EtO ii'a'irli 06111- Moial Ratio78.90 10.7 8.90 10.70 19.0 5.30 6.38 11.32 3.00 4.32 7.68 90 193 an.010. Ex.No. 1510 M0121 Ratio Ex. N0. 152b Resin to EtO Molal Ratio. I3.60 4.32: 7. 68 3.60 4 -12 .15. 68 .samplesdmewhzit.rubiiermandgelat-230 i 2' Ex. No. 153b inous but fairly soluble 12Eadiiy's6l- 100 171-0015.

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WAER-IN-OIL TYPE,CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFLERINCLUDING A HYDROPHILE QUATERNARY AMMONIUM COMPOUND OBTAINED BY REACTIONBETWEEN A DIMETHYLATED HIGHER ALIPHATIC AMINE IN WHICH THE HIGH MOLALRADICAL HAS AT LEAST 10 AND NOT MORE THAN 22 CARBON ATOMS, AND AN ESTERIN WHICH THE ACYL RADICAL IS THAT OF AN ALPHA-HALOGEN MONOCARBOXYLICACID HAVING NOT OVER 6 CARBON ATOMS AND THE ALCOHOLIC RADICAL IS THAT OFCERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID PHYDROPHILESYNTHETIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETAALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THECLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE,GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE,FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATERINSOLUBLE PHENOL-ALDEHYDE RESIN,SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRICPHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVETOWARDS SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCEOF TRIFUNCTIONAL PHENOLS; PHENOL BEING OF THE FORMULA: